Compound semiconductor and method for manufacturing same

ABSTRACT

A nitride compound semiconductor having a low resistivity that is conventionally difficult to be manufactured is provided. Since the nitride compound semiconductor exhibits a high electron mobility, a high-performance semiconductor device may be configured. The present invention may provide, at a high productivity, a group 13 nitride semiconductor of an n-type conductivity that may be formed as a film on a substrate having a large area size and has a mobility of 70 to 140 cm2/(V·s) by a pulsed sputtering method performed in a process atmosphere at room temperature to 700° C.

TECHNICAL FIELD

The present invention relates to a compound semiconductor and a method for manufacturing the same.

BACKGROUND ART

Devices using group 13 nitride semiconductors such as GaN and InN are now put into practical use in a wide range of products. Conventionally, an MOCVD method and an MBE method have been used for crystal growth of such a group 13 nitride semiconductor. However, the MOCVD method requires a process temperature exceeding 1000° C. The MBE method allows a compound semiconductor film to be formed at a low temperature, but is not suitable to mass manufacturing because there is a limit on the area size of the film that may be formed and the manufacturing cost is high.

With the MBE method, if donors are incorporated at a high concentration, absorption by the high concentration donor level generated in the forbidden band in the vicinity of the conduction band of the crystal structure occurs. For this reason, the MBE method has a problem that the transparency of the manufactured compound semiconductor film is decreased. For these reasons, the MOCVD method is now used to manufacture a compound semiconductor, mainly, to manufacture a nitride semiconductor for a practical use (Non-patent Document 1).

Currently, next-generation electronic devices having both a high withstand voltage and a low on-resistance are desired. In order to realize such an electronic device, it is desired to realize a two-, three-, or four-component compound semiconductor, more specifically, a compound semiconductor device using a group 13 nitride semiconductor. This requires further improvement in the quality of the crystal of such a compound semiconductor and improvement in the refinement of the doping technology. Especially for a vertical power device to be formed on a GaN substrate, it is urged to decrease the carbon concentration of an n-type drift layer and to improve the electron mobility. There are the following documents describing the prior art.

Patent Document 1 discloses a semiconductor device including a buffer layer formed of a metal nitride and a semiconductor layer, which are provided on a copper substrate.

Patent Document 2 discloses examples of a semiconductor substrate including a graphite plate having a thickness of 10 to 100 μm, containing a sintered polymer and having a heat resistance and flexibility, a buffer layer formed of HfN on the graphite plate, and a semiconductor layer formed of GaN on the buffer layer. Patent Document 3 discloses a method for manufacturing a group-III-V compound semiconductor by epitaxial growth on a ZnO substrate.

Patent Document 4 and Patent Document 5, which are regarding a nitride semiconductor, will be described in paragraph 0167 and thereafter in this specification.

Patent Document 6 is cited as a prior art document in the International Search Report for a PCT application described below (PCT/JP2017/020513 filed by the present applicant). Patent Document 6 discloses experimental results that indicate that even when the Si concentration is increased up to 2×10E+20/cm³, the AlGaN film is not roughened (FIG. 4).

Now, Non-patent Document 1 described above discloses research results on formation of a p-type GaN semiconductor layer. Non-patent Document 2 discloses research results on the contact resistance of a p-type GaN semiconductor layer. Non-patent Document 3 discloses results of a research for producing p-type GaN, for an LED device, based on InGaN by low-temperature growth by a PSD method. Non-patent Document 4 discloses research results on the electron mobility and the doping concentration regarding silicon.

Non-patent Document 5 discloses research results on a model of carrier mobility of GaN. Non-patent Document 6 discloses research results on evaluation of the contact resistance against a p-type GaN formed by the PSD method. Non-patent Document 7 discloses experiment examples of producing an LED on glass. Non-patent Document 8 discloses research results on a nitride single crystal grown by the PSD method. Non-patent Document 9 discloses a normally-off Ge-doped GaN transistor having an extremely low on-resistance.

Non-patent Document 10 discloses research results on Si-doped AlGaN having a low resistance and a high carrier concentration. Non-patent Document 11 discloses examples of experiments performed under the conditions that the Si concentration was 2×10¹⁶ cm⁻³ and the mobility was 1034 cm²/(V s). Non-patent Document 12 discloses an epitaxially grown film of GaN doped with Ge by the PSD method.

Non-patent Document 13 discloses, in detail, various characteristics of n-type GaN doped with Ge and Si that may provide new properties.

Finally, Non-patent Document 14 reports research results on fabrication of a high quality nitride semiconductor by a sputtering method and application thereof to devices.

CITATION LIST Patent Literature

-   Patent Document 1: Japanese Laid-Open Patent Publication No.     2008-243873 -   Patent Document 2: WO2011/021248A1 -   Patent Document 3: Japanese Laid-Open Patent Publication No.     2010-56435 -   Patent Document 4: Japanese Laid-Open Patent Publication No.     2016-115931 -   Patent Document 5: United States Patent Application Publication     2016/0172473 -   Patent Document 6: Japanese Laid-Open Patent Publication No.     2015-149342A

Non-Patent Literature

-   Non-patent Document 1: G. T. Zhao et al., “Optical Absorption and     Photoluminescence Studies of n-type GaN” Jpn. J. Appl. Phys. 38,     L933-L995 (1999) -   Non-patent Document 2: Arakawa et al., The Japan Society of Applied     Physics, 63rd Spring Meeting, 20p-H121-8 -   Non-patent Document 3: E. Nakamura et al., Appl. Phys. Lett. 104,     051121 (2014) -   Non-patent Document 4: D. M. Caughey et al.; Proc. IEEE 55, 2192     (1967) -   Non-patent Document 5: T. T, Mnatsakanov et al.; Solid-State     Electron. 47, 111 (2003) -   Non-patent Document 6: Proceedings, The Japan Society of Applied     Physics, 62nd Spring Meeting -   Non-patent Document 7: Nikkei Electronics, NE report, pp. 14-15,     Jul. 7, 2014 -   Non-patent Document 8: Fujioka “Flexible Device” project research     abstracts pp. 89-94 (published on Mar. 4, 2008) -   Non-patent Document 9: A. Suzuki et al., “Extremely low     on-resistance Enhancement-mode GaN-based HFET using Ge-doped     regrowth technique” (IEDM14, pp. 275-278 (2014)) -   Non-patent Document 10: Motoaki lwaya et al., “Extremely     low-resistivity and high-carrier-concentration Si-doped AlGaN with     low AlN molar fraction for improvement of wall plug efficiency of     nitride-based LED”, 2015 Conference on Lasers and Electro-Optics     Pacific Rim (Optical Society of America, 2015), paper 28C2_2 -   Non-patent Document 11: Ueno et all, “Development of n-type doping     technique for GaN by pulsed sputtering”, Proceedings, The Japan     Society of Applied Physics, 77th Autumn Meeting (2016) -   Non-patent Document 12: Ueno et al., “Highly conductive Ge-doped GaN     epitaxial layers prepared by pulsed sputtering”, Applied Physics     Express 10, 101002 (2017) -   Non-patent Document 13: Ueno et al., “Electron transport properties     of Degenerate n-type GaN prepared by pulsed sputtering”, APL     MATERIALS 5, 126102 (2017) -   Non-patent Document 14: Fujioka et al., “Growth of high quality     nitride semiconductors by sputtering and its application to device     fabrication”, Oyo Buturi, Vol. 86, No. 7, pp. 576-580 (2017)

SUMMARY OF INVENTION Technical Problem

With the conventional technology, in the case where it is attempted to realize crystal growth of a group 13 nitride semiconductor by the MOCVD method, carbon and hydrogen contained in the material gas are incorporated into the film. This causes a problem that it is difficult to form a high quality film having a low concentration of impurities such as carbon, hydrogen and the like.

In addition, in the case where it is attempted to realize crystal growth of a group 13 nitride semiconductor by the MOCVD method, it is generally difficult that a film having a donor concentration of 5×10¹⁹ cm⁻³ or higher exhibits an electron mobility of about 46 cm²/(V·s) or higher due to thermodynamic restrictions. The MOCVD method is based on a chemical reaction. Therefore, it is in fact impossible to realize crystal growth at a low temperature, and carbon and hydrogen contained in the material gas are easily incorporated into the manufactured film.

As a crystal growth method of a nitride semiconductor replacing the MOCVD method, a pulsed sputtering deposition (PSD) method is now proposed. It has been demonstrated that a p-type GaN thin film having a low concentration of residual hydrogen and exhibiting a high hole mobility is obtained by the PSD method (Non-patent Document 2).

Currently, the MOCVD method is used to manufacture an electronic device and a light emitting device on a nitride semiconductor substrate for practical use. However, it is difficult to manufacture, by the MOCVD method, an n-type layer having a high donor concentration which are important to decrease the resistance of these devices. Therefore, there are very few reports on the characteristics of such an n-type layer.

As can be seen, it is desired to develop a group 13 nitride semiconductor of n-type conductivity that exhibits a high electron mobility even in a region of a high donor concentration. In such a situation, it is required to realize a semiconductor material exhibiting as high an electron mobility as possible in order to achieve the purposes of improving the performance, saving the energy, and improving the efficiency of electronic devices and light emitting devices.

A research group of the present inventors proceeded research and development to raise the performance of nitride semiconductors, and published, as achievements thereof, “Development of low temperature fabrication process for nitride based LEDs” (The Japan Society of Applied Physics, 60th Spring Meeting, 30a-G21-10) (see FIG. 9), “Creation of function-expressing nanosystems by process integration” (JST Strategic Basic Research Programs (CREST) (see FIG. 10A and FIG. 10B), “Development of n-type doping technique for GaN by pulsed sputtering”, Proceedings, The Japan Society of Applied Physics, 77th Autumn Meeting, 13p-A21-3 (Autumn, 2016) (Non-patent Document 11, see FIG. 11), and the like.

The present invention, made in light of such a problem, has an object of easily manufacturing and providing a two-, three- or four-component compound semiconductor, more specifically, a group 13 nitride semiconductor film, of n-type conductivity that exhibits a high electron mobility even in a region of a high donor concentration.

The present inventors have disclosed a new nitride semiconductor and a method for manufacturing the same in a PCT application (Application No. PCT/JP2017/020513, Filing Date: Jun. 1, 2017; claiming priority based on Japanese Patent Application No. 2016-169994; Publication No. WO2018/042792A1, International Publication Date: Mar. 8, 2018).

The present invention includes a part overlapping of the examples in above-mentioned applications and also includes new examples.

Solution to Problem

In order to solve the above-described problems, the present invention provides [embodiment 1] to [embodiment 20] described below.

Embodiment 1

A two-, three-, or four-component compound semiconductor containing nitrogen and one element selected from the group consisting of B, Al, Ga and In, which are group 13 elements, wherein a combination of two property values of electron concentration and resistivity fulfills numerical value conditions enclosed by four points represented by:

(a) the electron concentration of 1.8×10²⁰ cm⁻³ and the resistivity of 0.25×10⁻³ Ω·cm,

(b) the electron concentration of 3.6×10²⁰ cm⁻³ and the resistivity of 0.25×10⁻³ Ω·cm,

(c) the electron concentration of 6×10²⁰ cm⁻³ and the resistivity of 0.15×10⁻³ Ω·cm, and

(d) the electron concentration of 3×10²⁰ cm⁻³ and the resistivity of 0.15×10⁻³ Ω·cm.

Alternatively, the combination of the two property values of electron concentration and resistivity may fulfill, instead of the numerical value conditions enclosed by the four points represented by (a) to (d) mentioned above, numerical value conditions enclosed by four points represented by:

(a-1) the electron concentration of 1.5×10²⁰ cm⁻³ and the resistivity of 0.20×10⁻³ Ω·cm,

(b-1) the electron concentration of 6×10²⁰ cm⁻³ and the resistivity of 0.20×10⁻³ Ω·cm,

(c-1) the electron concentration of 6×10²⁰ cm⁻³ and the resistivity of 0.10×10⁻³ Ω·cm, and

(d-1) the electron concentration of 4×10²⁰ cm⁻³ and the resistivity of 0.10×10⁻³ Ω·cm. Preferably, the resistivity is 0.18×10⁻³ Ω·cm or lower instead of the range having the upper limit mentioned in each of (a-1) to (d-1).

Embodiment 2

The compound semiconductor according to embodiment 1, wherein the resistivity is 0.190×10⁻³ Ω·cm or lower (limited to the case of (a) to (d)).

Embodiment 3

The compound semiconductor according to embodiment 1 or 2, further containing Si.

Embodiment 4

The compound semiconductor according to embodiment 1, 2 or 3, wherein the compound semiconductor has an RMS value, obtained by a surface roughness measurement by an AFM, of 1.5 nm or less.

Embodiment 5

The compound semiconductor according to embodiment 1, 2, 3 or 4, wherein the compound semiconductor has an n-type conductivity and an electron mobility of 80 cm²/(V·s) or higher.

Embodiment 6

The compound semiconductor according to any one of embodiments 1 to 5, wherein the compound semiconductor has an n-type conductivity and an electron mobility of 130 cm²/(V·s) or lower.

Embodiment 7

The compound semiconductor according to any one of embodiments 1 to 6, wherein the compound semiconductor contains Ga and N as main components.

Embodiment 8

The compound semiconductor according to any one of embodiments 1 to 7, wherein the compound semiconductor contains Ga as the group 13 element and further contains Al and/or In.

Embodiment 9

The compound semiconductor according to any one of embodiments 1 to 8, wherein the compound semiconductor contains Ge.

Embodiment 10

A contact structure, comprising a conductive portion containing the compound semiconductor according to any one of embodiments 1 to 9 and an electrode connected with each other.

Embodiment 11

A semiconductor device, comprising the contact structure according to embodiment 10.

Embodiment 12

A transparent electrode, comprising the compound semiconductor according to any one of embodiments 1 to 9.

Embodiment 13

A method for manufacturing a two-, three- or four-component compound semiconductor containing nitrogen and one element selected from the group consisting of B, Al, Ga and In, which are group 13 elements, the method comprising:

pulsed-sputtering a target metal containing at least Ga in a chamber in a process atmosphere containing noble gas, nitrogen gas and oxygen to form a film of the compound semiconductor having a resistivity of 0.4×10⁻³ Ω·cm or lower with a growth rate of 450 nm/h or less.

Embodiment 14

The method for manufacturing the compound semiconductor according to embodiment 13, wherein a substrate temperature for a formation of the film is 700° C. or lower.

Embodiment 15

The method for manufacturing the compound semiconductor according to embodiment 13 or 14, wherein the growth rate is set to 90 to 450 nm/h. In this embodiment, it is preferred to set the growth rate to 100 to 400 nm/h, and it is more preferred to set the growth rate to 180 to 370 nm/h.

Embodiment 16

The method for manufacturing the compound semiconductor according to embodiment 13, 14 or 15, wherein oxygen gas is supplied to the process atmosphere.

Embodiment 17

The method for manufacturing the compound semiconductor according to any one of embodiments 13 to 16, wherein the sputtering is performed using an oxygen component contained in a component remaining in the chamber or using trace amount of oxygen component contained in another material gas or the target metal, without supplying oxygen gas into the chamber.

Embodiment 18

The method for manufacturing the compound semiconductor according to any one of embodiments 13 to 17, wherein a distance between a surface on which the compound semiconductor is formed and the target metal is set to 10 to 50 cm. The distance is more preferably set to 15 to 30 cm.

Embodiment 19

A sputter gun usable for the method for manufacturing the compound semiconductor according to any one of embodiments 13 to 18, wherein:

the target metal is provided in a head of the sputter gun, and the head is incorporated into the chamber so as to face a substrate electrode, and the head has an effective size of about 1 inch to about 4 inches.

Embodiment 20

The sputter gun according to embodiment 19, wherein the target metal has a circular or rectangular planar shape and is mounted on the head.

Four new experiment examples according to the present invention are shown in FIG. 1 to FIG. 3. In FIG. 1, the relationship between the growth rate of GaN doped with Si (horizontal axis) and the electron concentration of a film of the obtained compound semiconductor is plotted. FIG. 1 shows the relationship between the growth rate and the electron concentration in a high concentration region in which the electron concentration is 2×10²⁰ cm⁻³ or higher. FIG. 2 shows a similar relationship except that the vertical axis represents the resistivity.

Based on these four experiment examples, the present inventors performed fitting on the lower limit of the resistivity from the scatter data on the growth rate and the resistivity, and obtained the predicted value of 0.083 mΩ·cm (see FIG. 3).

Assuming that the usable effective growth rate by a sputtering device currently used commercially is 59 nm/h, the result of about 0.1 mΩ·cm was obtained from the intersection of this growth rate with the fitting line. It is considered that the resistivity of 0.1 mΩ·cm is fully feasible by adjusting, for example, the material and the process conditions to be used, in this manner.

According to the present invention, in order to realize a film of a compound semiconductor having desired properties, various conditions may be adjusted to gradually find a required growth rate, and such a growth rate may be set to a value suitable to mass production. For example, according to one conceivable technique, the structure of the chamber, and the shape and the locations of the electrodes are determined, and then, the inner pressure of the chamber, the back pressure (performance of the vacuum pump), the type of gas to be used, the flow of the gas, the control on the impurity gas, the control on the magnetic field, the power source, the substrate temperature, the distance between the target and the substrate, and the like, which are parameters for the film formation operation, are optimized. The processes that may be commonly performed in sputtering, for example, pre-washing, drying, heating and the like may be performed when necessary. In addition, various characteristics of the formed film sample, for example, the thickness, the state (surface roughness, cross-sectional structure), the optical characteristics, the conductivity, the mechanical characteristics, and the like of the film may be evaluated at high precision. In this manner, the film formation operation according to the present invention may be managed properly.

FIG. 4 is a scatter graph of the resistivity and the electron concentration of the high concentration n-type GaN doped with Ge or Si disclosed by the present inventors in Non-patent Document 13. FIG. 5 is a scatter graph in which data in the experiment examples newly added in this application is plotted in addition to the data in FIG. 4. In FIG. 5, the star marks represent the results in the new experiment examples. It is understood that one of the experiment examples shows a numerical value equivalent to that of the previous experiment examples, whereas the other experiment examples show that the resistivity is decreased as compared with in the previous experiment examples.

FIG. 6A and FIG. 6B are each an enlargement of a part of FIG. 5. A region that is the subject of the present invention described in the present application is represented with a dashed line (see regions X₁ and X₂ in FIG. 6A and FIG. 6B). The border between region X₁ and region X₂ (these regions will also be collectively referred to as “region X”) is a line at which the resistivity is 0.190 mΩ·cm.

The corners of parallelogram including regions X₁ and X₂ have coordinate values of (1.8×10E+20: 0.25 mΩ·cm), (3.6×10E+20: 0.25 mΩ·cm), (3.0×10E+20: 0.15 mΩ·cm) and (6.0×10E+20: 0.15 mΩ·cm). In the region enclosed by these four points, the mobility is about 70 to about 140 cm²/(V·s). It is easy to stably manufacture a high concentration n-type compound semiconductor by controlling three parameters of the resistivity, the mobility and the electron concentration. A product corresponding to the conditions represented by region X₁ or region X₂ may be manufactured in accordance with the value of the resistivity required by the use or the specifications. In FIG. 6A and FIG. 6B, two points represented by small squares (squares including “*”) in region X₁ correspond to the experiment examples disclosed in Non-patent Document 13 mentioned above. In this manner, a high concentration n-type compound semiconductor exhibiting desired properties may be manufactured by adjusting the production conditions represented by region X.

FIG. 7 and FIG. 8 are graphs showing various characteristics (electron mobility, temperature dependence, and the like) of the high concentration n-type GaN shown in Non-patent Document 13. In FIG. 7, the vertical axis represents the electron mobility, and the horizontal axis represents the electron concentration. Hereinafter, the present invention including a first invention (invention of the application based on which the present application claims priority) and a second invention (addition in the PCT application) disclosed in the above-mentioned PCT application will be described.

According to embodiment 1, it is indispensable to fulfill the numerical value range conditions enclosed by the four points mentioned in (a) to (d) or (a-1) to (d-1).

In each of the above-described embodiments of the present invention, it is preferred that the following structures are provided.

In each of the embodiments, it is preferred that the absorption coefficient is 2000 cm⁻¹ or less to light having a wavelength region of 405 nm. In each of the embodiments, it is preferred that the absorption coefficient is 1000 cm⁻¹ or less to light having a wavelength region of 450 nm.

According to the present invention, the term “two-component nitride” refers to a compound of one element among B, Al, Ga and In, and nitrogen. Namely, the “two-component nitride” is a two-component mixed crystal of BN (boron nitride), AlN (aluminum nitride), GaN (gallium nitride) or InN (indium nitride).

A three-component nitride refers to a compound obtained as a result of any one of the two-component group 13 elements mentioned above being partially replaced with another group 13 element. The three-component nitride is, for example, a three-component mixed crystal of InGaN (indium gallium nitride), AlGaN (aluminum gallium nitride), or AlInN (aluminum indium nitride). Regarding the three-component compound, it is known that the composition ratio thereof may be adjusted to adjust the bandgap within the range of the characteristics of the two-component compound.

Even a compound containing a trace amount of another group 13 element in addition to the group 13 element acting as a main component of the compound semiconductor may also be encompassed in the scope of the above-described invention. Combinations of elements are arbitrary as long as the effects of the present invention are not impaired.

Another invention having a different combination of elements is directed to a nitride semiconductor that contains nitrogen and at least one group 13 element selected from the group consisting of B, Al, Ga and In, has an n-type conductivity, and has an electron concentration and a resistivity fulfilling the numerical value conditions enclosed by the four points mentioned in (a) to (d) or (a-1) to (d-1) in embodiment 1.

In an embodiment of the present invention, a preferred numerical value range is, for example, a resistivity of 0.20×10⁻³ Ω·cm or lower and an electron mobility of 70 to 140 cm²/(V·s).

A more preferable numerical value range is a predetermined range of a resistivity of 0.18×10⁻³ Ω·cm or lower and 0.15×10⁻³ Ω·cm or higher and an electron mobility of 70 to 140 cm²/(V·s) (see region X₁ in FIG. 6A and FIG. 6B).

Preferably, the nitride semiconductor has a contact resistance of 1×10⁻⁴ SIcm² or lower against an n-type ohmic electrode metal.

In an embodiment, the nitride semiconductor contains oxygen as an impurity at 1×10¹⁷ cm⁻³ or higher.

Preferably, the nitride semiconductor has an absorption coefficient of 2000 cm⁻¹ or less to light having a wavelength region of 405 nm. Preferably, the nitride semiconductor has an absorption coefficient of 1000 cm⁻¹ or less to light having a wavelength region of 450 nm. Preferably, the nitride semiconductor has an RMS value of 5.0 nm or less obtained by a surface roughness measurement performed by an AFM.

In an embodiment, the at least one group 13 element is Ga.

In an embodiment, the nitride semiconductor contains either one of, or both of, Si and Ge as donor impurities.

The above-described invention is applicable to a contact structure, comprising the nitride semiconductor for a conductive portion.

The above-described invention is also applicable to a contact structure, comprising the nitride semiconductor for an electrode. Such a contact structure is usable in a semiconductor device.

Advantageous Effects of Invention

A nitride compound according to the present invention exhibits a low resistivity of 0.25×10⁻³ Ω·cm or lower even in a high electron concentration range of about 1.8×10²⁰ cm⁻³ or higher, and also shows an electron mobility of 70 cm²/(V·s) or higher.

It should be noted that there are cases where a low resistivity of 0.19×10⁻³ Ω·cm or lower is almost unnecessary, depending on the specification, the use or the like of the semiconductor device. In such cases, the conditions for the manufacturing process (gas, cathode power, electron concentration of the target) may be adjusted in consideration of the productivity to manufacture a compound semiconductor having a resistivity of about 0.20 to about 0.25×10⁻³ Ω·cm, and adapt the compound semiconductor to a structure portion in which the device is required.

According to the present invention, the pulsed sputtering method (PSD method) is used to form a sputtered single crystal film with no high-temperature process. More preferably, a compound semiconductor film is formed in a process performed generally at room temperature. There is no limit on the area size of the substrate, and films of various sizes from a small size to a large size may be manufactured.

For example, a compound semiconductor film of a rectangular outer shape having a length of a side of 2 inches or longer or a compound semiconductor film of a circular outer shape having a diameter of 2 inches or longer may be formed. Alternatively, a compound semiconductor film having an area size that is 30 cm² or larger and having an allowable area within the restriction of the internal space of the sputtering apparatus may be formed.

In this case, a high quality compound semiconductor film is easily formed with no need of a buffer layer, which is required by the conventional technology.

Now, the properties of the compound semiconductor according to the present invention will be described. The resistivity ρ of an n-type nitride semiconductor film is in inverse proportion to the electron mobility μ_(n) and the carrier concentration n (p=(q·n·p_(n))). However, in the present invention, the n-type nitride semiconductor film exhibits a high electron mobility even at a high electron concentration. This indicates that a high quality film having a low electric resistance is formed. Namely, the present invention provides a high quality group 13 nitride semiconductor film easily usable for a semiconductor device. The compound semiconductor according to the present invention has a threading dislocation density of about 1×10⁶/cm² to about 5×10¹⁰/cm². A nitride compound film preferably having a threading dislocation density of 10⁵/cm² or lower, namely, in the order of 10³ to 10⁴/cm², may be manufactured.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a graph showing the relationship between the electron concentration and the growth rate according to the present invention.

FIG. 2 is a graph showing the relationship between the resistivity and the growth rate according to the present invention.

FIG. 3 is a graph showing exponential fitting performed on the resistivity and the growth rate according to the present invention.

FIG. 4 is a scatter graph of the electron concentration and the resistivity according to the present invention.

FIG. 5 is a scatter graph of the electron concentration and the resistivity of high concentration n-type nitride semiconductors according to the present invention and the conventional art.

FIG. 6A is a scatter graph of the electron concentration and the resistivity of the high concentration n-type nitride semiconductors (enlarged graph).

FIG. 6B is a scatter graph of the electron concentration and the resistivity of the high concentration n-type nitride semiconductors (graph with additional information).

FIG. 7 is a graph, according to the present invention, showing the experimental results on the electron mobility of high concentration n-type GaN as a function of the electron concentration (n(RT)) and also showing the electron mobility that is calculated by expression (1) with the compensation ratio θ being changed (cited from Non-patent Document 13: APL MATERIALS 5, 126102 (2017), “Electron transport properties of degenerate n-type GaN prepared by pulsed sputtering”).

FIG. 8(a) is a graph, according to the present invention, showing the temperature dependence of the electron mobility of Si-doped GaN in the case where the electron concentration is 3.3×10²⁰ cm⁻³ at room temperature; FIG. 8(b) is a graph showing the temperature dependence of the electron mobility and the fitting curve of Si-doped samples and Ge-doped samples; and FIG. 8(c) is a graph showing the nonparabolic coefficient α and the compensation ratio θ, obtained by fitting, as a function of the electron concentration at room temperature (cited from Non-patent Document 13: APL MATERIALS 5, 126102 (2017), “Electron transport properties of degenerate n-type GaN prepared by pulsed sputtering”).

FIG. 9 (FIG. 1) shows a surface AFM image of an Mg-doped GaN thin film; and FIG. 9 (FIG. 2) is a graph provided to evaluate the activation energy of an Mg acceptor (cited from Proceedings, The Japan Society of Applied Physics, 60th Spring Meeting, 30a-G21-10, 15-190).

FIG. 10A(a) shows an optical micrograph, and FIG. 10A(b) shows an IV curve, both of an AlGaN/GaN hetero-junction FET manufactured by a PSD method (cited from the final research report of “Creation of function-expressing nanosystems by process integration”, which is a research field of CREST, Japan Science and Technology Agency).

FIG. 10B(a) shows the relationship between the electron concentration and the electron mobility of GaN thin films manufactured by a pulsed sputtering deposition method; and FIG. 10B(b) shows the temperature dependence of the hole concentration of Mg-doped GaN (cited from the final research report of “Creation of function-expressing nanosystems by process integration”, which is a research field of CREST, Japan Science and Technology Agency).

FIG. 11 is a graph showing the relationship between the electron concentration (N_(e)) and the electron mobility (p_(e)) of an Si-doped n-type GaN film manufactured by a PSD method.

FIGS. 12(a) and 12(b) provide graphs of SIMS data each showing a profile, in a depth direction, of the oxygen concentration of a GaN film having an Si concentration of 2×10²⁰ cm⁻³.

FIGS. 13(a) and 13(b) show AFM images of surfaces of the Si-doped GaN films shown in FIGS. 12(a) and 12(b) formed by sputtering.

FIGS. 14(a) and 14(b) provide graphs respectively showing the absorption coefficient and the refractive index of a GaN film having an Si concentration (electron concentration) of 2×10²⁰ cm⁻³ measured by an ellipsometer.

FIGS. 15(A) and 15(B) provide a schematic view (A) and a schematic view in a planar direction (B) each showing a crystal structure of GaN.

FIG. 16A is a schematic view showing a structure of a sputtering apparatus usable in the present invention.

FIG. 16B is a schematic side view of a sputter gun used in the present invention.

FIG. 17 is a graph showing an example of pulse sequence to be applied to an electrode of the sputtering apparatus at the time of sputtering according to the present invention.

FIG. 18 is a schematic vertical cross-sectional view showing an inner structure of a sputtering apparatus usable in the present invention.

FIG. 19 is a schematic cross-sectional view of a semiconductor device according to embodiment 1 of the present invention.

FIG. 20 is a schematic cross-sectional view showing a contact structure according to embodiment 2 of the present invention.

FIG. 21 is a schematic cross-sectional view showing a contact structure according to embodiment 3 of the present invention.

FIG. 22 is a schematic cross-sectional view of a thin film transistor to which the present invention is applicable.

FIG. 23 is a schematic cross-sectional view of an AlGaN/GaN HEMT to which the present invention is applicable.

FIG. 24 is a schematic cross-sectional view of an LED device to which the present invention is applicable.

FIG. 25 is a schematic cross-sectional view of a surface emitting laser device to which the present invention is applicable.

FIG. 26 shows the relationship between the electron concentration and the resistivity of GaN according to the present invention.

FIG. 27 shows the relationship between the concentrations of donor impurities and the electron concentrations, of the GaN according to the present invention, obtained by a SIMS measurement.

FIGS. 28(a), 28(b), 28(c), and 28(d) provide AFM images of surfaces of Ge-doped GaN samples as examples of surface state of GaN.

FIG. 29 is a schematic cross-sectional view of a vertical power MOSFET.

FIG. 30 is a schematic cross-sectional view of a GaN-based LED.

FIG. 31 is a schematic cross-sectional view of a Schottky diode.

DESCRIPTION OF EMBODIMENTS

Hereinafter, a compound semiconductor manufactured by pulsed sputtering using a group 13 nitride semiconductor will be described as an embodiment according to the present invention with reference to the drawings.

A group 13 nitride semiconductor according to an embodiment of the present invention is formed as a film by a pulsed sputtering deposition method (PSD method).

(Pulse Sputtering Method)

The “pulsed sputtering method (PSD method)” used to manufacture a compound semiconductor of a nitride according to the present invention, and the materials and the manufacturing method used to manufacture the compound semiconductor, are basic items well known to a person of ordinary skill in the art.

For example, the standard technologies disclosed in the following publications are usable to work the present invention with no problem: “Growth of a nitride substrate and a lattice-matched substrate and device characteristics” (CMC Publishing Co., Ltd.; first edition published on Oct. 30, 2009), “New development of high frequency semiconductor materials and devices” (CMC Publishing Co., Ltd.; first edition published on Nov. 13, 2006), “Improvement in performance of next-generation power semiconductors and industrial development thereof” (CMC Publishing Co., Ltd.; first edition published on Jun. 10, 2015), Japanese Laid-Open Patent Publication No. 2009-138235 “Pulse sputtering apparatus, and pulsed sputtering method”, Japanese Laid-Open Patent Publication No. 2014-159368 “Gallium nitride sintered body or gallium nitride molded article, and method for producing the same”, and the like. Patent Documents 2 and 3, and Non-patent Documents 3 and 4, and the like may also be referred to.

According to the PSD method used in the present invention, crystal growth is carried out based on a physical reaction, and therefore, may be performed at a low temperature. In addition, carbon and hydrogen in a film formation environment are conspicuously removable. Since the crystal growth may be performed at a low temperature, generation of a thermal stress in the film is suppressed, and also a compound easily leading to phase separation such as, for example, InGaN, is stably grown.

Single crystal growth of a compound semiconductor according to the present invention is not visually recognizable directly, but the principle of action of the crystal growth is generally considered as follows. FIG. 15 shows a crystal structure of GaN, which is one of two-component group 13 compounds. During the film formation of a compound semiconductor according to the present invention, it is considered that a polar surface at which Ga atoms of GaN are located to form a hexagonal shape (Ga atom surface) is aligned to a surface of a substrate acting as an underlying layer, so that a single crystal structure is formed.

In this step, with the manufacturing method used in the present invention, the film formation is allowed to be performed at a relatively low temperature, instead of at a high temperature exceeding 1000° C. required by the MOCVD method or the like. The temperature range to be used is 700° C. or lower and may include room temperature of 25° C. (room temperature to 700° C.). Although the temperature varies in accordance with the film formation rate, a preferable temperature range may be, for example, 300 to 700° C.

For this reason, it is estimated that a small number of oxygen atoms contained in the film formation atmosphere are present to cover a surface of the film to be formed during the film formation. It is considered that as a result of the above, the oxygen atoms act to prevent the bonding of the group 13 element and nitrogen, and therefore, the film formation process advances while main elements to form the desired compound are kept free.

In addition, it is considered that since the film formation conditions are the same for the entirety of the underlying layer in a planar direction, a crystal structure that is uniform and has a high level of crystallinity entirely is formed.

The GaN compound semiconductor formed as a sputtered film in this manner is considered to gradually grow in an axial direction of the hexagonal shape (thickness direction of the film), so that in a final step, a compound semiconductor film that is uniform in the plane and has at least a certain area size is manufactured.

It is preferred that the underlying layer to be used is formed of a material fulfilling the condition of having a lattice matched with, or matched in a pseudo manner with, the compound semiconductor to be grown. The film formation process by the PSD method is not performed at a high temperature exceeding 1000° C. Therefore, the material of the underlying layer does not need to be resistant against a high temperature. However, in order to improve the crystallinity, it is preferred that the crystal and the underlying layer fulfill the conditions of being lattice-matched or pseudo-lattice-matched with each other.

For the above-described reasons, according to the present invention, it is especially preferred that the material of the underlying layer is selected from the four types: SiC, sapphire, GaN, single crystalline silicon. Sapphire has a heat resistant temperature of 1200° C., and single crystalline silicon has a heat resistant temperature of 1100° C. These materials are usable to manufacture semiconductor devices such as AlGaN/GaN HEMTs, full-color LEDs, InGaN-TFTs, sensors and the like.

Alternatively, the material of the underlying layer may be, for example, metal foil or alkali-free glass for FPD having a heat resistant temperature of 600 to 700° C., or the like, although the formed crystal quality of the compound semiconductor is inferior to the quality in the case where the above-listed materials are used. In this case, it is preferred that a buffer layer is formed on a surface of the material of the underlying layer for the crystal growth, for the purpose of making the underlying layer pseudo-lattice-matched with the compound semiconductor.

Regarding the size of the film to be formed according to the present invention, a device having a length of a shorter side or a diameter of a circle of 2 inches to 10 inches may be manufactured. The present invention is also applicable to a medium-sized device having a diagonal line of a rectangle of 10 to 30 inches and a large device having a diagonal line of a rectangle of 30 inches or longer. The device or the substrate acting as the underlying layer may be circular, square, rectangular, or of an asymmetrical shape.

FIG. 16A, FIG. 16B and FIG. 17 show a schematic view of a sputtering apparatus and a pulse sequence usable to manufacture a compound semiconductor according to the present invention. A sputtering apparatus 1 mainly includes a chamber 11, a substrate electrode 12, a target electrode 13, a DC power supply 14, a power supply controller 15, a nitrogen supply source 16, a heating device 17, an argon supply source 18 and the like.

The chamber 11 is sealable against the outside. The inner pressure of the chamber 11 is allowed to be decreased by a vacuum pump or the like (not shown). The substrate electrode 12 is located in the chamber 11, and is capable of holding a heat dissipation sheet 12 a.

A sputter source (or a sputter gun) 13 includes a cylindrical head 13 b on which a sputter material 13 a is placed, and a shaft 13 c connected with the cylindrical head 13 b. A power source line 13 d is provided in the shaft 13 c. An effective size of the head is about 1 inch to about 4 inches. The sputter source 13 is provided in the chamber 11 so as to face the substrate electrode 12, and is capable of holding the target 13 a.

A distance between a surface of the substrate and the sputter source 13 is represented by L_(H). In an embodiment of the present invention, distance L_(H) may be set to about 10 to about 50 cm. Distance L_(H) is more preferably set to 15 to 40 cm, and is still more preferably set to 20 to 30 cm.

The target 13 a is formed of a compound of a group 13 element and nitrogen. A high quality target material with little impurities that is commonly available at present is used. For example, a high quality material such as five nine or six nine is needed. The shape and the size of the sputter gun may be adjusted when necessary in accordance with the type of the target to be used. For a batch process, for example, a circular target having a long diameter or a linear (rectangular) target may be used. Needless to say, a plurality of sputter guns may be located in the chamber. A film of a compound semiconductor according to the present invention may be formed either with a target of Ga, Al or Si or with a target of GaN or AlN.

The DC power supply 14 is electrically connected with the substrate electrode 12 and the sputter source 13, and is a voltage source that applies a DC voltage between the substrate electrode 12 and the sputter source 13.

The power supply controller 15 is connected with the DC power supply 14, and performs control regarding the timing of the operation of the DC power supply 14. The power supply controller 15 allows a pulse voltage to be applied between the substrate electrode 12 and the sputter source 13.

The nitrogen supply source 16 is connected with the inside of the chamber 11 by, a supply tube or the like, and supplies nitrogen gas into the chamber 11. The argon supply source 18 supplying argon gas is provided to generate plasma required for sputtering.

An oxygen supply source that supplies a predetermined amount of oxygen is also provided. The internal pressure is constantly allowed to be monitored while the film is formed. The content of oxygen in the chamber needs to be controlled to be kept at about 10 ppm nearly constantly during the film formation of the compound semiconductor. Alternatively, the sputtering may be performed while the content of oxygen contained as impurities in main supply gas is controlled. Still alternatively, the approximate amount of an oxygen component contained in trace amount in the other materials may be estimated, so that the amount of the oxygen component contained in the nitride semiconductor may be suppressed to be within a predetermined level in the entire process.

In order to realize this, it is indispensable that the chamber used for the pulsed sputtering, the supply system of the process gas and the discharge system of the process gas (main discharger, rough discharger) prohibit gas leak and invasion of external air, and it is important that the pressure is controlled to be highly stable during the film formation. It is considered to be fundamental to supply a trace amount of oxygen into the chamber intentionally. In order to realize this, the chamber needs to be confirmed to have been cleaned, and the materials to be used need to have a high purity.

The heating device 17 is secured to, for example, the substrate electrode 12, so that the temperature around the heat dissipation sheet 12 a on the substrate electrode 12 can be adjusted. The representative examples of the film formation conditions to be used according to the present invention are as follows. FIG. 7 is an example of pulse sequence. The voltage P_(A) of the driving pulse is adjustable. The film formation rate is generally 0.1 to 4 nm/sec. on average, and more preferably 0.2 to 2 nm/sec. The film formation rate is 0.025 nm/sec. to 0.125 nm/sec. in a high concentration region in which the electron concentration is 2×10²⁰ cm⁻³.

(a) Driving method: pulsed sputtering method (PSD method)

(b) Duty ratio: 5%

(c) Average power: 100 V

(d) Pulse frequency: 1 kHz

(e) Growth pressure: 2×10⁻³ Torr

(f) Dopant: Si

The film formation by the sputtering was performed in atmospheric gas containing argon as a main component, and the substrate temperature during the film formation was set to the range of 300 to 700° C. In this case, doping gas such as SiH₄, GeH₄ or the like is usable as the doping material, and a target containing Si or Ge atoms is usable, in order to form a high concentration n-type group 13 nitride compound semiconductor.

Experiments were made in which oxygen were incorporated at a concentration of 10 ppm into the atmospheric gas to be used for the sputtering in order to introduce oxygen into the film of the target compound semiconductor to be manufactured, and in which oxygen was not incorporated. Physical characteristics of the compound semiconductor manufactured with oxygen and the compound semiconductor manufactured with no oxygen were checked in comparison with each other.

FIG. 18 is a schematic vertical cross-sectional view of a continuous film formation apparatus 10 of a roll-to-roll system. A plurality of film formation chambers 5 are provided inside the continuous film formation device 10. The present invention is applicable to such a device as long as the substrate film 4 is a metal foil or a very thin film-like glass substrate that may be taken into a roll or taken out of a roll. While the flexible substrate film 4 is transported in a horizontal direction from a take-out roll 2 to a take-in roll 3, the sputtering may be performed toward the substrate film 4 at a plurality of locations in the film formation chamber. As a result, a semiconductor device containing a desired compound semiconductor or the like is processed at a high speed. The table in the chamber is usable for, for example, a diameter of 320 to 600 mm. In a roll-to-roll process, there is a high possibility that the growth rate changes moment by moment. In such a case, an effective growth rate may be assumed for management. The growth rate is considered to be generally lower than in a batch process.

According to the present invention, crystal growth of a compound semiconductor is realized on an underlying layer or a substrate having an area size defined by a shorter side of a rectangle or a diameter of at least 2 inches. The crystal is manufactured at a low temperature and at a high rate so as to have a certain area size and to be uniform. In addition, a novel compound semiconductor is mass-manufactured while the manufacturing cost thereof is suppressed.

FIG. 11 shows the relationship between the electron concentration (N_(e)) and the electron mobility (μ_(e)) of an Si-doped n-type GaN film manufactured by the PSD method by the present inventors. The electron concentration and the electron mobility were measured by a room temperature Hall effect measurement. In the experiment example providing data plotted in this figure, about 2×10²⁰ cm⁻³ or the vicinity thereof is the upper limit. The electron concentration (N_(e)) is considered to be substantially equal to the Si donor concentration. The film formation by the sputtering was performed in atmospheric gas containing argon gas as a main component, and the substrate temperature during the film formation was in the range of 300 to 700° C.

Oxygen was incorporated at a concentration of 10 ppm into the atmospheric gas to be used for the sputtering for the purpose of introducing oxygen into this film, so that a crystal film exhibiting single crystallinity was formed. An n-type ohmic electrode metal stack structure (Ti (20 nm)/AI (60 nm)/Ti (20 nm)/Au (50 nm)) was formed on a surface of the resultant GaN thin film, and was annealed in nitrogen at 700° C. The contact resistance of samples formed in this manner was evaluated by a TLM method and was found to be 8.5×10⁻⁵ Ω·cm².

In this figure, the circles show the actually measured values, and the curve shows the fitting result based on the Caughey-Thomas-type empirical formula (formula 1 below; see Non-patent Document 4), which is used to describe the mobility in a low electric field. In the formula below, N_(D) is the donor concentration. Since the electron concentration (N_(e)) is considered to be substantially equal to the Si donor concentration as described above, the fitting is performed with an assumption that N_(D)=N_(e).

μ=μ_(min)+[μ_(max)−μ_(min)]/[1+(N _(D) /N _(R))^(γ)]  (1)

From the above-shown fitting result,

μ_(max)=1034 cm²/(V·s),

μ_(min)=125 cm²/(V·s)

were found. These values are comparable to the highest value of the mobility of the n-type GaN thin film formed by the MOCVD method conventionally reported (see, for example, Non-patent Document 5). As can be seen, it has been confirmed that the carrier scattering is sufficiently suppressed in the film of the compound semiconductor manufactured according to the present invention.

With the MOCVD method of the conventional technology, it is considered to be difficult to form a GaN thin film exhibiting such a high electron mobility when the donor concentration is generally 5×10¹⁹ cm⁻³ or higher. According to the present invention, as shown in FIG. 11, the Si-doped n-type GaN film manufactured by the PSD method exhibits the values matching the Caughey-Thomas-type empirical formula (Non-patent Document 4) even at the donor concentration of at least 2×10²⁰ cm⁻³.

Namely, it has been found out that an n-type GaN film according to this example manufactured by the PSD method is a very high quality film exhibiting an electron mobility of 46 cm²/(V·s) or higher even at an electron concentration of 5×10¹⁹ cm⁻³ or higher. Preferably, a film exhibiting an electron mobility of 50 cm²/(V·s) or higher is usable. The resistivity ρ of an n-type nitride semiconductor film is in inverse proportion to the electron mobility μ_(n) and the carrier concentration n. Therefore, the n-type nitride semiconductor film exhibits a high electron mobility even at a high electron concentration. This indicates that a high quality film having a low resistance is formed.

The samples shown in FIG. 11 are all Si-doped. The impurity to be incorporated as a donor is not limited to Si and may be Ge or the like.

When the donor concentration of the nitride semiconductor film is increased in order to realize a high electron concentration, the transparency of the film to visible light is decreased. This causes a concern that an inconvenience may occur in the case where the nitride semiconductor film according to the present invention is used for a transparent electrode or the like.

Under such circumstances, according to the present invention, the decrease in the transparency caused by the increase in the electron concentration of the film of the compound semiconductor is compensated for as follows. The nitrogen site is replaced, so that oxygen, which is a dopant acting as a donor, is incorporated as an impurity to expand the bandgap of the film.

The bandgap of an oxygen-doped film depends on the amount of doping. For example, in the case of GaN, the bandgap at room temperature may be varied in the range of 3.4 eV to 4.9 eV (value of the bandgap of gallium oxide). In the case of, for example, GaN, when oxygen is incorporated as an impurity at 1×10¹⁷ cm⁻³ or higher into the film, the bandgap at room temperature is generally about 3.4 to about 3.6 eV.

Such an effect of oxygen, for example, allows the nitride semiconductor film according to this example to have an absorption coefficient of 2000 cm⁻¹ or less to light having a wavelength region of 405 nm or to have an absorption coefficient of 1000 cm⁻¹ or less to light having a wavelength region of 450 nm. In this manner, the nitride semiconductor film according to this example is usable for a transparent electrode with no inconvenience.

FIG. 12 provides graphs each showing an oxygen concentration of the GaN film according to this embodiment manufactured by the PSD method. FIG. 12(b) shows SIMS data representing a profile, in a depth direction, of the oxygen concentration of a GaN film having an Si concentration of 2×10²⁰ cm⁻³, among the samples shown in FIG. 11. It is understood that the oxygen is contained at a concentration of about 1 to 3×10¹⁸ cm⁻³. This film exhibits an electron mobility of 110 cm²/(V·s).

The RMS value of an AFM image representing the surface roughness of this film was 3.97 nm as seen from FIG. 13(b). The present inventors performed an AFM measurement on the film samples formed by the present inventors at various electron concentrations and containing oxygen at an electron concentration of 5×10¹⁹ cm⁻³ or higher. All the samples had an RMS value of 5.0 nm or less.

In the meantime, crystal growth was performed under substantially the same conditions but with no incorporation of 10 ppm oxygen into the atmospheric gas. The results were as follows. As shown in the profile in FIG. 12(a), the oxygen concentration was about 1×10¹⁶ cm⁻³, and the mobility at this point was 45 cm²/(V·s). As seen from FIG. 13(a), the RMS value representing the surface roughness of this thin film was 14.1 nm.

Now, the two conditions, namely, the condition of incorporating oxygen and the condition of not incorporating oxygen, will be discussed. In the case with oxygen, it is considered that oxygen atoms in the atmosphere covering a surface of the film that is being formed cause the stress to be alleviated and the migration of the atoms at the surface to promote. It is considered that such suppression of the surface roughness avoids introduction of point defects and thus improves the mobility. At a high temperature used by the MOCVD method or the like of the conventional technology, oxygen evaporates from the surface. Therefore, it is considered to be difficult to provide the effect of improving the quality realized by the low-temperature growth performed by the PSD method.

By contrast, in the case with no oxygen, it is considered that the above-described action is not easily provided and thus the crystal of the film formed by the PSD method is likely to include defects.

FIG. 14 provides graphs showing the absorption coefficient (FIG. 14(a)) and the refractive index (FIG. 14(b)) of a GaN film having an Si concentration (electron concentration) of 2×10²⁰ cm⁻³ measured by an ellipsometer. This film exhibits an electron mobility of 115 cm²/V·s. This film has an absorption coefficient of 844 cm⁻¹ at a wavelength of 450 nm, which is used for a blue LED as a standard wavelength, and has an absorption coefficient of 1860 cm⁻¹ at a wavelength of 405 nm, which is used for a blue-violet laser as a standard wavelength.

As can be seen, the oxygen doping allows the film to have an absorption coefficient of 2000 cm⁻¹ or less to light having a wavelength region of 405 nm or to have an absorption coefficient of 1000 cm⁻¹ or less to light having a wavelength region of 450 nm. As a result, the obtained compound semiconductor is usable as a transparent material.

Hereinafter, various forms of electronic device to which a compound semiconductor according to the present invention is applicable.

Embodiment 1

FIG. 19 is a schematic cross-sectional view of a compound semiconductor device 20 including a group 13 nitride semiconductor formed on a substrate. Reference sign 21 represents the substrate (sapphire), and reference sign 22 represents GaN.

Embodiment 2

FIG. 20 is a schematic cross-sectional view of a contact structure formed using a compound semiconductor according to the present invention. Reference sign 31 represents a GaN substrate, reference sign 32 represents GaN (film of a compound semiconductor formed by the PSD method), reference sign 34 represents an insulating film, reference sign 33 represents a wiring electrode connectable with an external device, and reference sign 35 represents a contact hole.

Embodiment 3

FIG. 21 is a schematic cross-sectional view of a contact structure 40 formed using a group 13 nitride compound semiconductor according to the present invention. In FIG. 21, reference sign 41 represents an n-type GaN contact layer, reference sign 42 represents a Ti layer, reference sign 43 represents an Al layer, reference sign 44 represents an Ni layer, and reference sign 45 represents an Au layer. In this example, a composite metal electrode is used. After the film formation, heat treatment is performed at about 900° C.

Application Examples

FIG. 22 is a schematic cross-sectional view of a thin film transistor to which the present invention is applicable. A high concentration n-type GaN layer is applicable as a contact layer of an electrode of the thin film transistor.

In the figure, reference sign 51 represents a substrate formed of alkali-free glass or the like, reference sign 52 represents an interlayer insulating layer, reference sign 53S represents a source-side contact layer (high concentration n⁺ GaN layer), reference sign 54S represents a source region, reference sign 55 represents an active layer, reference sign 54D represents a drain region, reference sign 53D represents a drain-side contact layer (high concentration n⁺ GaN layer), reference sign 56 represents a gate oxide film, reference sign 57 represents a source electrode, reference sign 58 represents a gate electrode, and reference sign 59 represents a drain electrode. The source region 54S and the drain region 54D are each formed such that the concentration of the impurity is gradually changed between the corresponding contact layer and the active layer.

FIG. 23 is a schematic cross-sectional view of a HEMT to which the present invention is applicable. A high concentration n-type GaN layer according to the present invention is applicable as contact layers located below, and in contact with, source and drain electrodes of the AlGaN/GaN-HEMT. In the figure, reference sign 61 represents a substrate formed of GaN, sapphire, SiC, Si or the like, reference sign 62 represents a buffer layer formed of GaN, AlN or the like, reference sign 63 represents a GaN undoped layer, reference sign 64 represents an AlGaN barrier layer, and reference sign 65 represents a contact layer formed using a high concentration n-type GaN layer. A source electrode 66, a gate electrode 67 and a drain electrode 68 are provided in a top part of the HEMT.

In the thin film transistor (FIG. 22) and the HEMT (FIG. 23) described above, the high concentration n-type GaN layer is applicable as the contact layer. The contact resistance of such a contact layer against an electrode in a circuit element in which an operating current flows (the circuit element is each of source and drain in the thin film transistor and the HEMT) is significantly decreased. This significantly contributes to the improvement in performance of the electronic device.

FIG. 24 is a schematic cross-sectional view of an LED device as an example of GaN-based semiconductor device to which the present invention is applicable.

As shown in this figure, a plurality of compound semiconductor layers are sequentially stacked from the side of a substrate 71 formed of GaN, sapphire, SiC or Si. A buffer layer 72, an n-type GaN layer 73, a GaInN/GaN MQW light emitting layer 74, a p-type GaN layer 75, a tunnel junction 76 including a p-type InGaN layer 76 a and a high concentration n-type GaN layer 76 b, an n-type GaN layer 77, a contact layer 78 formed of a high concentration n-type GaN layer, and electrodes 79A and 79B are provided.

FIG. 25 is a schematic cross-sectional view of an InGaN/GaN VCSEL (surface emitting laser) structure to which the present invention is applicable. In such a vertical cavity surface emitting laser (VCSEL), a resonator is formed to be perpendicular to a surface of a semiconductor substrate. Therefore, laser light is output perpendicularly to the substrate surface.

In the figure, reference sign 81 represents a GaN substrate, reference sign 82D represents an inner multi-layer reflection mirror, reference sign 83 represents an n-type GaN layer, reference sign 84 represents an MQW active layer formed of GaInN/GaN, reference sign 85 represents a p-type AlGaN layer, reference sign 86 a represents a p-type InGaN layer, and reference sign 86 b represents a high concentration n-type GaN layer. 86 a and 86 b form a tunnel junction 86. Reference sign 87 represents an n-type GaN layer, reference sign 88 represents a high concentration n-type GaN layer (contact layer), reference sign 89A and 89B represent electrodes, and reference sign 82U represents an upper multi-layer reflection mirror.

As described above, the compound semiconductor according to the present invention is usable for, for example, regions of a light emitting device or an electronic device in which a large amount of electric current flows, a contact portion of a semiconductor device, or an electrode structure such as a transparent electrode or the like. The compound semiconductor according to the present invention is preferably usable for a wire or the like of an electronic device drivable at a very low voltage. The compound semiconductor according to the present invention is adaptable to the specifications of large electric current and large electric power, which are not easily dealt with by the conventional technology.

The compound semiconductor according to the present invention exhibits a high electron mobility and thus has a low resistance, and therefore is considered to contribute to improvement in the operation speed of devices.

So far, a compound semiconductor according to the first invention, namely, a two-, three- or four-component compound semiconductor that contains nitrogen and one element selected from the group consisting of B, Al, Ga and In, which are group 13 elements, contains oxygen as an impurity at 1×10¹⁷ cm⁻³ or higher, has an electron concentration of 5×10¹⁹ cm⁻³ or higher, has n-type conductivity and exhibits an electron mobility of 46 cm²/(V·s) or higher has been described.

Hereinafter, a nitride semiconductor according to a second invention made by the present inventors will be described.

The nitride semiconductor has a conspicuous feature of exhibiting a lower resistivity (namely, exhibiting a higher mobility) than a conventional semiconductor although being in the form of a crystal doped with a donor at a high concentration.

Specifically, the nitride semiconductor contains nitrogen and at least one group 13 element selected from the group consisting of B, Al, Ga and In, has n-type conductivity, exhibits an electron concentration of 1×10²⁰ cm⁻³ or higher, and exhibits a resistivity of 0.3×10⁻³ Ω·cm or lower. Preferably, the at least one group 13 element is Ga, and either one of, or both of, Si and Ge are contained as donor impurities.

Conventionally, a nitride semiconductor doped with Ge grown by the MBE method at a high concentration and exhibiting a relatively low resistivity is known. As compared with such a nitride semiconductor, the nitride semiconductor according to the present invention realizes a lower resistivity in a region having a higher electron concentration.

Such a nitride semiconductor exhibiting a low resistivity (exhibiting a high mobility) although being in the form of a crystal doped with donors at a high concentration is expected to be used for various uses, for example, to decrease the parasitic resistance of an electronic device such as an HEMT or the like, to provide a material replacing a transparent conductive film of ITO or the like, and to realize cascade connection of LED modules.

FIG. 26 shows the relationship between the electron concentration (cm⁻³) and the resistivity (mΩ·cm) of GaN according to the present invention. In the figure, star marks represent the GaN according to the present invention. Among the star marks, white star marks represent Si-doped GaN, and gray star marks represent Ge-doped GaN. The figure also shows, for comparison, data of GaN obtained by the MOCVD method (diamond-shaped marks) and the MBE method (circular marks) reported so far, and also shows the relationship between the electron concentration and the resistivity obtained by a theoretical calculation. In the figure, θ represents the compensation ratio of the concentration of ionized impurities (ratio of the acceptor concentration N_(A) and the donor concentration N_(D); N_(A)/N_(D)). (Note: FIG. 26 is the same as FIG. 4 of Non-patent Document 13 mentioned above except for one experiment example having the lowest resistivity shown in a bottom part of the graph.)

The GaN crystal conventionally reported exhibits a tendency that the resistivity is decreased as the electron concentration is increased regardless of whether the crystal is obtained by the MBE method or the MOCVD method. However, the resistivity is increased when the electron concentration is above a certain level.

For example, in the case of GaN obtained by the MOCVD method, Si-doped GaN shows an increase in the resistivity when the electron concentration exceeds about 5×10¹⁹ cm⁻³, and Ge-doped GaN shows an increase in the resistivity when the electron concentration exceeds about 1×10²⁰ cm⁻³. In the case of GaN obtained by the MBE method, Si-doped GaN shows an increase in the resistivity when the electron concentration exceeds about 1.5×10²⁰ cm⁻³, and Ge-doped GaN shows an increase in the resistivity from when the electron concentration exceeds about 5×10²⁰ cm⁻³.

By contrast, in the case of GaN according to the present invention, neither Si-doped GaN (white marks) nor Ge-doped GaN (gray marks) shows any such increase in the resistivity even when the electron concentration is 5×10²⁰ cm⁻³.

In addition, in the case of the conventional GaN, even Ge-doped GaN, obtained by the MBE method and exhibiting the lowest resistivity in a region of a high electron concentration, exhibits a resistivity of merely 0.4 mΩ·cm (0.4×10⁻³ Ω·cm) at the minimum at an electron concentration of about 5×10²⁰ cm⁻³. By contrast, the GaN according to the present invention exhibits a resistivity of 0.2 mΩ·cm (0.2×10⁻³ Ω·cm) at nearly the same electron concentration.

As is clear from the results shown in this figure, unlike the conventional GaN, the GaN according to the present invention has a feature of exhibiting a conspicuously low resistivity of 0.3×10⁻³ Ω·cm or lower especially when the electron concentration is 1×10²⁰ cm⁻³ or higher, and this feature is not lost even when the electron concentration is 2×10²⁰ cm⁻³ or higher. As shown in the table below, this tendency has been experimentally confirmed in the range of resistivity down to 0.16×10⁻³ Ω·cm. The theoretical value of the lowest limit of the resistance value caused by scattering of ionized impurities is 0.04×10⁻³ Ω·cm, but is varied to, for example, 0.2×10⁻³ Ω·cm, 0.15×10⁻³ Ω·cm, 0.1×10⁻³ Ω·cm or the like depending on the film formation conditions or the like. As a result of the fitting shown in FIG. 3, the estimated value of 0.083×10⁻³ Ω·cm was obtained.

FIG. 27 shows the relationship between the concentration of the donor impurities and the electron concentrations, of the GaN according to the present invention, obtained by a SIMS measurement. It is understood from these results that the activation ratio of the donors is about 1 in the GaN according to the present invention obtained by the PSD method. Namely, it is understood that for the GaN according to the present invention, the electron concentration is controllable by merely controlling the doping concentration of the donor impurity.

The various characteristics (electron concentration, electron mobility, resistivity, and surface roughness) of the GaN according to the present invention are shown in Table 1 (Si-doped GaN) and Table 2 (Ge-doped GaN). Table 3 (Si-doped GaN) shows the relationship between the growth rate and various characteristics (electron concentration, electron mobility, resistivity, surface roughness) of Si-doped GaN in a high concentration region according to the present invention.

TABLE 1 Si-doped GaN Electron Electron Surface roughness concentration mobility Resistivity RMS value (cm⁻³) (cm²V⁻¹s⁻¹) (mΩ · cm) (nm) 1.12E+19 211 2.64 0.85 2.16E+19 159 1.82 0.95 3.02E+19 154 1.34 0.94 4.75E+19 150 0.876 0.70 8.09E+19 136 0.567 0.90 9.36E+19 128 0.521 0.88 1.44E+20 126 0.344 0.65 1.47E+20 126 0.337 0.75 1.66E+20 115 0.327 0.55 1.93E+20 106 0.305 0.88 1.99E+20 110 0.285 0.95 2.03E+20 110 0.279 0.68 2.95E+20 108 0.196 0.76 3.30E+20 107 0.177 0.81 3.84E+20 99.6 0.165 0.88 3.95E+20 100 0.160 0.91

TABLE 2 Ge-doped AlGaN Electron Electron Surface roughness concentration mobility Resistivity RMS value (cm⁻³) (cm²V⁻¹s⁻¹) (mΩ · cm) (nm) 1.24E+19 153 3.29 0.91 2.03E+20 96.8 0.280 0.77 2.87E+20 82.1 0.265 0.62 3.04E+20 79.0 0.260 0.62 3.24E+20 74.6 0.258 0.54 3.28E+20 77.4 0.246 0.46 3.36E+20 73.8 0.252 0.46 3.39E+20 70.2 0.262 0.31 3.54E+20 72.2 0.244 0.34 3.99E+20 73 0.214 0.35 4.11E+20 70.4 0.216 0.65 4.35E+20 70.9 0.202 0.65 4.49E+20 66.2 0.210 0.55 4.70E+20 66.2 0.200 0.55 5.15E+20 60.1 0.202 0.86 5.25E+20 57.8 0.207 0.86 5.49E+20 41.3 0.275 0.86

TABLE 3 Si-doped GaN Electron Electron Surface Growth rate concentration mobility Resistivity roughness (nm/h) (cm⁻³) (cm²V⁻¹s⁻¹) (mΩ · cm) (nm) 200 3.95E+20 100 0.158 0.78 230 3.30E+20 105 0.180 0.66 280 2.86E+20 119 0.183 0.85 364 2.08E+20 110 0.273 0.68

The GaN layers shown in Table 1 to Table 3 were all obtained in nearly the same conditions as the crystal growth conditions by the PSD method described above. The materials and the like each having the following purity were used. The electron concentration was changed by changing the power applied to the cathode from 20 to 150 W.

Substrate temperature during the growth: 600 to 700° C.

Sputtering target (Si): single crystal having a purity of 99.999%

Sputtering target (Ge): single crystal having a purity of 99.99%

Ga: Purity: 99.99999%

Nitrogen gas: purity: 99.9999%

The present inventors note that the vacuum level of the film formation environment and the quality of the vacuum state are important for growing a high quality crystal, and appropriately adjusted the conditions of pulsed sputtering (pulse voltage, pulse width, duty ratio, etc.) in order to obtain a crystal of a desired film quality. It is one of advantages of the PSD method that such fine adjustments may be made quickly.

The measurement conditions and the like for the above-mentioned various properties are as follows.

The electron concentration and the electron mobility were measured by use of a Hall measurement device (ResiTest8400, Toyo Corporation) while the applied current was varied in the range of 1 mA to 10 mA and the applied magnetic field was varied in the range of 0.1 to 0.5 T (tesla) in accordance with the resistivity of the sample. The temperature for the measurement was room temperature.

The surface roughness was measured by use of an AFM device (JSPM4200 produced by JEOL Ltd.).

FIG. 28 shows AFM images of surfaces of the Ge-doped GaN samples as examples of surface state of the above-described GaN. These samples all have an RMS value less than 1 nm. In general, a surface having an RMS value, obtained by a surface roughness measurement by an AFM device, of 5.0 nm or less may be evaluated to be sufficiently flat. In consideration of this, it is understood that the nitride semiconductor according to the present invention has a highly flat surface.

Nitride semiconductor crystals having the Ga site of GaN be partially replaced with Al or In (AlGaN or InGaN) were also manufactured, and various properties thereof were examined. The results are shown in Table 4 and Table 5. In these samples, the concentration of Al or In was 1%. The purity and the like of each of the materials used for the crystal growth are as follows.

Substrate temperature during the growth: 600 to 700° C.

Sputtering target (Si): single crystal having a purity of 99.999%

Sputtering target (Ge): single crystal having a purity of 99.99%

Ga: Purity: 99.99999%

Al: Purity: 99.999%

In: Purity: 99.999%

Nitrogen gas: purity: 99.9999%

TABLE 4 Ge-doped AlGaN Electron Electron concentration mobility Resistivity (cm⁻³) (cm²V⁻¹s⁻¹) (mΩ · cm) 4.76E+20 61.7 0.213

TABLE 5 Si-doped InGaN Electron Electron concentration mobility Resistivity (cm⁻³) (cm²V⁻¹s⁻¹) (mΩ · cm) 2.32E+20 98.4 0.273

The contact resistance of each of the nitride semiconductors shown in Table 1 to Table 5 was measured. It has been confirmed that all the samples have a contact resistance of 1×10⁻⁴ Ω·cm² or lower against an n-type ohmic electrode metal. Such a value is sufficiently low. A contact structure including any of the above-described nitride semiconductors for a conductive portion is expected to be used in various uses, for example, to decrease the parasitic resistance of an electronic device such as a HEMT or the like, to provide a material replacing a transparent conductive film of ITO or the like, and to realize cascade connection of an LED module.

The contact resistance was measured by use of a TLM (Transmission Line Model) measurement apparatus (semiconductor parameter analyzer Agilent 4155C) on a TLM pattern including Ti/Al/Ti/Au electrode structures (100 μm×100 μm) located at an inter-electrode distance of 2 μm to 100 μm.

As described above, the nitrogen site of the nitride semiconductor may be replaced, so that oxygen, which is a dopant acting as a donor, is incorporated as an impurity to expand the bandgap of the film. In this manner, the decrease in the transparency caused by the increase in the electron concentration of the film of the nitride semiconductor is compensated for.

For this purpose, for example, oxygen as an impurity is incorporated at 1×10¹⁷ cm⁻³ or higher into the above-described nitride semiconductor. Such incorporation of oxygen as an impurity allows the nitride semiconductor to have an absorption coefficient of 2000 cm⁻¹ or less to light having a wavelength region of 405 nm or to have an absorption coefficient of 1000 cm⁻¹ or less to light having a wavelength region of 450 nm.

The above-described nitride semiconductor according to the present invention is formed by the PSD method. The present inventors consider that the above-described characteristics are obtained for the following reason: with other crystal growth methods, the crystal growth is carried out in a thermal equilibrium state, whereas with the PSD method, the crystal growth is carried out in a thermal non-equilibrium state.

A nitride semiconductor such as GaN or the like doped with a donor at a high concentration is thermodynamically unstable, and therefore, is partially decomposed even while the crystal growth is being carried out. Namely, the growth and the decomposition of the crystal occur at the same time. Therefore, the donor impurity once incorporated into the crystal is pushed out at the time of decomposition. When it is attempted to dope the nitride semiconductor with donor impurities at a high concentration, this phenomenon that the donor impurities are pushed out reaches to an unignorable level, and as a result, the crystallinity itself is decreased. Namely, in the case where the nitride semiconductor is doped with the donor impurity at a high concentration, the decrease in the crystallinity is unavoidable under the crystal growth conditions close to the thermal equilibrium state.

By contrast, with the PSD method, the crystal growth is carried out in a thermal non-equilibrium state. Therefore, the donor impurity is not easily pushed out, and thus the crystallinity is not easily decreased.

In general, the Ge donor impurities tend to be more easily incorporated into the nitride semiconductor crystal at a high concentration than the Si donor impurities. One conceivable reason for this is the following. Since the radius of the Ge ion is close to the radius of Ga ion, the Ge ion easily replaces the Ga ion site. As a result, the accumulation of stress in the nitride semiconductor film is alleviated, and thus the surface of the film tends to be flat.

As described above, the nitride semiconductor according to the present invention realizes a lower resistivity in a region of a higher electron concentration than the conventional nitride semiconductor.

There are the following documents that disclose inventions relating to a nitride semiconductor device having a low on-resistance.

Japanese Laid-Open Patent Publication No. 2016-115931 (Patent Document 4) discloses an invention relating to a nitride semiconductor device having a low on-resistance. Paragraph 0049 describes that “as described above, the source-side nitride semiconductor regrowth layer 205 a and the drain-side nitride semiconductor regrowth layer 206 a each may contain n-type impurities at a high concentration. However, as shown in FIG. 4, when the impurity is silicon (Si), even if an impurity amount to be supplied during the growth of a nitride semiconductor layer is increased, the carrier concentration of the impurity in the nitride semiconductor layer to be formed is not increased. That is, the impurity carrier concentration has a certain upper limit. On the other hand, when germanium (Ge) is used as the impurity, a higher carrier concentration than that of silicon can be realized”.

Paragraph 0095 describes that “in order to investigate the characteristics of the composite electrode of the nitride semiconductor device 200 thus formed, the sheet resistance of the nitride semiconductor regrown layer itself and the contact resistance thereof with the 2DEG were measured by a transmission line measurement (TLM) method. FIG. 7 shows the relationship between the sheet resistance of the nitride semiconductor regrown layer itself and the supply amount of Ge. It was found that when the flow rate ratio of TEGe to TMG is increased to 0.09 or more with an increase in supply amount of TEGe, a nitride semiconductor regrown layer having a lowered sheet resistance of approximately 1.5×10⁻⁶ Ω·cm can be obtained. It was found that when a nitride semiconductor regrown layer formed under the conditions described above is used, the nitride semiconductor device 200 has a contact resistance of 1 to 5×10⁻⁶ Ω·cm, and a preferable contact with the 2DEG can be obtained”.

Patent Document 4 and the corresponding United States Patent Application Publication US2016/0172473 (Patent Document 5) filed claiming the benefit of priority to Patent Document 4 were compared against each other regarding the above description. As a result, it has been found out that the name and the unit of the vertical axis of FIG. 7 are variously changed. It is presumed that Patent Document 4 includes some typographical error.

A technological document written by the inventors of Patent Document 4 (IEDM14: Non-patent Document 9), pp. 275-278 (“Extremely low on-resistance Enhancement-mode GaN-based HFET using Ge-doped regrowth technique”) will be referred to. This document discloses a Ge-doped nitride semiconductor regrowth layer exhibiting a low on-resistance. FIG. 3 is exactly the same as FIG. 7 of Patent Document 4.

The vertical axis is labeled as “Specific contact resistance (Ω·cm²)”. Regarding FIG. 3, there is a description “the measured specific contact resistance as a function of TEGe supply is shown in FIG. 3, where extremely low specific contact resistance of 1.5×10⁻⁶ Ω·cm² was achieved”. For this reason, it is considered that the vertical axis of FIG. 7 of Patent Document 4 should be “contact resistance” and the unit should be “Ω·cm²”.

If, as shown in FIG. 7 of Patent Document 4, the resistivity is about 1.5×10⁻⁶ Ω·cm and the Ge concentration (electron concentration) is 1×10²⁰ cm⁻³, the electron mobility is about 42,000 cm²/(V·s). This value is far from the normal value known as the electron mobility of GaN crystal (about 1,200 cm²/(V·s)). Based on this also, it is obvious that the above-described portion includes typographical errors.

As described above, Patent Document 4 is considered to disclose a “nitride semiconductor regrowth layer having a lowered contact resistance of approximately 1.5×10⁻⁶ Ω·cm²”.

The above-described nitride semiconductor according to the present invention has a feature of exhibiting a low resistivity (exhibiting a high mobility) although being in the form of a crystal doped with donors at a high concentration, and utilizing such a feature, is expected to be used for various uses, for example, to decrease the parasitic resistance of an electronic device such as an HEMT or the like, to provide a material replacing a transparent conductive film of ITO or the like, and to realize cascade connection of an LED module. For example, the nitride semiconductor according to the present invention may be applied as follows.

[Application to a Vertical Power MOSFET]

FIG. 29 is a schematic cross-sectional view of a vertical power MOSFET. This vertical power MOSFET 100 includes an n⁺-GaN layer 105 of a nitride semiconductor, according to the present invention, formed on a stack structure including an n⁺-GaN layer 102, an n⁻-GaN layer 103 and a p-GaN layer 104. The n⁺-GaN layer 105 according to the present invention may be patterned as follows. After being deposited on the entire surface, the n⁺-GaN layer is patterned by lithography. Alternatively, a selective growth technology may be used, according to which, a crystal surface of gallium nitride is exposed to only a part of a surface of the sample, and the n⁺-GaN layer is epitaxially grown selectively on the exposed part. Reference sign 106 represents an insulating film, reference sign 101 represents a drain, reference sign 107 represents a source, and reference sign 108 represents a gate.

[Application to an LED]

FIG. 30 is a schematic cross-sectional view of a GaN-based LED. The LED 200 includes an n-type nitride semiconductor layer 202, an active layer 203 including a quantum well layer, a p-type nitride semiconductor layer 204, and an n⁺-GaN layer 205 according to the present invention sequentially stacked on a substrate 201 formed of a nitride semiconductor.

A cathode electrode 206 is formed on a region of the n-type nitride semiconductor layer 202 that is exposed as a result of the n⁺-GaN layer 205, the p-type nitride semiconductor layer 204 and the active layer 203 being partially removed. An anode electrode 207 is formed above the p-type nitride semiconductor layer 204 with the n⁺-GaN layer 205 being located therebetween. The n⁺-GaN layer 205 according to the present invention is conductive with the p-type nitride semiconductor layer 204 via a tunnel junction.

[Application to a Schottky Diode]

FIG. 31 is a schematic cross-sectional view of a Schottky diode. In this Schottky diode 300, an n⁺-GaN substrate 301 has an n⁺-GaN layer 306 according to the present invention formed on a rear surface thereof. An n⁻-GaN layer 302 is formed on a front surface of the n⁺-GaN substrate 301. An ohmic electrode 303 is formed on the n⁺-GaN layer 306 side, and a Schottky electrode 304 is formed on the n⁻-GaN layer 302 side. In the figure, reference sign 305 represents an insulating film.

The nitride semiconductor according to the present invention exhibiting a low resistivity (exhibiting a high mobility) although being in the form of a crystal doped with a donor at a high concentration is usable for an n⁺-GaN layer of, for example, an IGBT (Insulated Gate Bipolar Transistor) in addition to the above-described devices.

As described above, the compound semiconductor according to the second invention made by the present inventors may be summarized as follows.

The second invention is directed to a nitride semiconductor having n-type conductivity and containing nitrogen and at least one group 13 element selected from the group consisting of B, Al, Ga and In, in which the nitride semiconductor has an electron concentration of 1×10²⁰ cm⁻³ or higher and exhibits a resistivity of 0.3×10⁻³ Ω·cm or lower.

Preferably, the electron concentration is 2×10²⁰ cm⁻³ or higher.

Preferably, the nitride semiconductor has a contact resistance of 1×10⁻⁴ Ω·cm² or lower against an n-type ohmic electrode metal.

In an embodiment, the nitride semiconductor contains oxygen as an impurity at 1×10¹⁷ cm⁻³ or higher.

Preferably, the nitride semiconductor has an absorption coefficient of 2000 cm⁻¹ or less to light having a wavelength region of 405 nm.

Preferably, the nitride semiconductor has an absorption coefficient of 1000 cm⁻¹ or less to light having a wavelength region of 450 nm.

Preferably, the nitride semiconductor has an RMS value of 5.0 nm or less obtained by a surface roughness measurement performed by an AFM.

In an embodiment, the at least one group 13 element is Ga.

In an embodiment, the nitride semiconductor contains either one of, or both of, Si and Ge as donor impurities.

The lower limit of the resistivity is, for example, 0.2×10⁻³ Ω·cm, 0.15×10⁻³ Ω·cm, or 0.1×10⁻³ Ω·cm.

The relationship between the electron concentration and the resistivity of the nitride semiconductor fulfills a numerical value range enclosed by four points at which (a) the electron concentration is 1×10²⁰ cm⁻³ and the resistivity is 0.3×10⁻³ Ω·cm, (b) the electron concentration is 3×10²⁰ cm⁻³ and the resistivity is 0.3×10⁻³ Ω·cm, (c) the electron concentration is 4×10²⁰ cm⁻³ and the resistivity is 0.15×10⁻³ Ω·cm, and (d) the electron concentration is 9×10²⁰ cm⁻³ and the resistivity is 0.15×10⁻³ Ω·cm.

The above-described invention is applicable to a contact structure, comprising the nitride semiconductor for a conductive portion. The above-described invention is also applicable to a contact structure, comprising the nitride semiconductor for an electrode. Such a contact structure is usable in a semiconductor device.

The present invention has an object of realizing a compound semiconductor having properties in a range partially overlapping that of the preferred numerical value range of the high concentration n-type GaN disclosed in the above-mentioned PCT application and also having a resistivity in a range lower than that in the PCT application.

Embodiment 1 of the present invention provides a two-, three-, or four-component compound semiconductor containing nitrogen and one element selected from the group consisting of B, Al, Ga and In, which are group 13 elements. A combination of two property values of electron concentration and resistivity fulfills numerical value conditions enclosed by four points represented by:

(a) the electron concentration of 1.8×10²⁰ cm⁻³ and the resistivity of 0.25×10⁻³ Ω·cm,

(b) the electron concentration of 3.6×10²⁰ cm⁻³ and the resistivity of 0.25×10⁻³ Ω·cm,

(c) the electron concentration of 6×10²⁰ cm⁻³ and the resistivity of 0.15×10⁻³ Ω·cm, and

(d) the electron concentration of 3×10²⁰ cm⁻³ and the resistivity of 0.15×10⁻³ Slam.

Alternatively, embodiment 1 of the present invention provides a compound semiconductor fulfilling the numerical value conditions enclosed by the four points mentioned in (a-1) to (d-1) mentioned above. Specifically, embodiment 1 of the present invention is directed to a nitride semiconductor containing GaN as a main component.

An embodiment of the present invention regarding a manufacturing method provides a method for manufacturing a two-, three- or four-component compound semiconductor containing nitrogen and one element selected from the group consisting of B, Al, Ga and In, which are group 13 elements. The method includes:

pulsed-sputtering a target metal containing at least Ga in a chamber in a process atmosphere containing noble gas, nitrogen gas and oxygen to form a film of the compound semiconductor having a resistivity of 0.4×10⁻³ Ω·cm or lower with a growth rate of 450 nm/h or less.

A compound semiconductor exhibiting desired property values in accordance with the specifications or the use within the numerical value conditions enclosed by (a) to (d) may be manufactured. It is easy to choose the numerical value conditions from region X. For a use that does not require a compound semiconductor having a very low resistivity, a compound semiconductor matching the conditions of region X₂ may be manufactured and used. In the case where a low resistivity is particularly required, a compound semiconductor matching the conditions of region X₁ may be manufactured and used.

INDUSTRIAL APPLICABILITY

The two-, three- or four-component nitride semiconductor according to the present invention fulfills the numerical value conditions enclosed by (a) to (d) or (a-1) to (d-1) to exhibit a superb, namely, low resistivity or a high electron mobility that has not been realized by the conventional art.

The present invention is applicable to an important circuit element that determines the performance of an electronic circuit, such as a contact portion of a wiring structure that is included in an electronic device having a low electric resistance and requiring a large amount of electric current, for example, a horizontal or vertical power semiconductor device such as a HEMT or the like, a high withstand voltage diode, a thin film transistor, a display device or the like, an active layer or the like.

The nitride semiconductor according to the present invention is usable for a high-speed communication device, a computation device, a solar cell, a control circuit, an electronic device for au automobile or the like in addition to the power semiconductor device, the display device and the light emitting device.

REFERENCE SIGNS LIST

-   -   1 Sputtering apparatus     -   2 Take-out roll     -   3 Take-in roll     -   4 Substrate film     -   5 Film formation chamber     -   10 Continuous film formation apparatus     -   11 Chamber     -   12 Substrate electrode     -   13 Sputter Source     -   14 DC power supply     -   15 Power supply controller     -   16 Nitrogen supply source     -   17 Heating device     -   12 a Heat dissipation sheet     -   21 Substrate     -   22 GaN     -   31 Substrate     -   32 GaN     -   33 Insulating layer     -   34 Insulating layer     -   35 Contact hole     -   41 n-type GaN contact layer     -   42 Ti layer     -   43 Al layer     -   44 Ni layer     -   45 Au layer     -   100 Vertical power MOSFET     -   101 Drain     -   102 n⁺-GaN layer     -   103 n⁻-GaN layer     -   104 p-GaN layer     -   105 n⁺-GaN layer     -   106 Insulating film     -   107 Source     -   108 Gate     -   200 LED     -   201 Substrate     -   202 n-type nitride semiconductor layer     -   203 Active layer     -   204 p-type nitride semiconductor layer     -   205 n-side electrode     -   206 p-side electrode     -   300 Schottky diode     -   301 n⁺-GaN layer     -   302 n⁻-GaN layer     -   303 Ohmic electrode     -   304 Schottky electrode     -   305 Insulating film     -   306 n⁺-GaN layer 

1. A two-, three-, or four-component compound semiconductor containing nitrogen and one element selected from the group consisting of B, Al, Ga and In, which are group 13 elements, wherein a combination of two property values of electron concentration and resistivity fulfills numerical value conditions enclosed by four points represented by: (a) the electron concentration of 1.8×10²⁰ cm⁻³ and the resistivity of 0.25×10⁻³ Ω·cm, (b) the electron concentration of 3.6×10²⁰ cm⁻³ and the resistivity of 0.25×10⁻³ Ω·cm, (c) the electron concentration of 6×10²⁰ cm⁻³ and the resistivity of 0.15×10⁻³ Ω·cm, and (d) the electron concentration of 3×10²⁰ cm⁻³ and the resistivity of 0.15×10⁻³ Ω·cm.
 2. The compound semiconductor according to claim 1, wherein the resistivity is 0.190×10⁻³ Ω·cm or lower.
 3. The compound semiconductor according to claim 1, further containing Si.
 4. The compound semiconductor according to claim 1, wherein the compound semiconductor has an RMS value, obtained by a surface roughness measurement by an AFM, of 1.5 nm or less.
 5. The compound semiconductor according to claim 1, wherein the compound semiconductor has an n-type conductivity and an electron mobility of 80 cm²/(V·s) or higher.
 6. The compound semiconductor according to claim 1, wherein the compound semiconductor has an n-type conductivity and an electron mobility of 130 cm²/(V·s) or lower.
 7. The compound semiconductor according to claim 1, wherein the compound semiconductor contains Ga and N as main components.
 8. The compound semiconductor according to claim 1, wherein the compound semiconductor contains Ga as the group 13 element and further contains Al and/or In.
 9. The compound semiconductor according to claim 1, wherein the compound semiconductor contains Ge.
 10. A contact structure, comprising a conductive portion containing the compound semiconductor according to claim 1 and an electrode connected with each other.
 11. A semiconductor device, comprising the contact structure according to claim
 10. 12. A transparent electrode, comprising the compound semiconductor according to claim
 1. 13. A method for manufacturing a two-, three- or four-component compound semiconductor containing nitrogen and one element selected from the group consisting of B, Al, Ga and In, which are group 13 elements, the method comprising: pulsed-sputtering a target metal containing at least Ga in a chamber in a process atmosphere containing noble gas, nitrogen gas and oxygen to form a film of the compound semiconductor having a resistivity of 0.4×10⁻³ Ω·cm or lower with a growth rate of 450 nm/h or less.
 14. The method for manufacturing the compound semiconductor according to claim 13, wherein a substrate temperature for a formation of the film is 700° C. or lower.
 15. The method for manufacturing the compound semiconductor according to claim 13, wherein the growth rate is set to 90 to 450 nm/h.
 16. The method for manufacturing the compound semiconductor according to claim 13, wherein oxygen gas is supplied to the process atmosphere.
 17. The method for manufacturing the compound semiconductor according to claim 13, wherein the sputtering is performed using an oxygen component contained in a component remaining in the chamber or using trace amount of oxygen component contained in another material gas or the target metal, without supplying oxygen gas into the chamber.
 18. The method for manufacturing the compound semiconductor according to claim 13, wherein a distance between a surface on which the compound semiconductor is formed and the target metal is set to 10 to 50 cm.
 19. A sputter gun usable for the method for manufacturing the compound semiconductor according to claim 13, wherein: the target metal is provided in a head of the sputter gun, and the head is incorporated into the chamber so as to face a substrate electrode, and the head has an effective size of about 1 inch to about 4 inches.
 20. The sputter gun according to claim 19, wherein the target metal has a circular or rectangular planar shape and is mounted on the head. 